TID-4005(Pt. 2b) SUMMARIES OF THE USAEC BASIC RESEARCH PROGRAM IN CHEMISTRY (ON SITE ) August 1964 Division of Research, AEC UNITED STATES ATOMIC ENERGY COMMISSION Division of Technical Information LEGAL NOTICE This report was prepared as an account of Government sponsored work. Neither the United States, nor the Commission, nor any person acting on behalf of the Commission: A. Makes any warranty or representation, expressed or implied, with respect to the accu- racy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus, method, or process disclosed in this report. 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SUMMARIES OF THE USAEC BASIC RESEARCH PROGRAM IN CHEMISTRY (On Site) Division of Research, AEC Indexes prepared by Division of Technical Information Extension August 1964 UNITED STATES ATOMIC ENERGY COMMISSION Division of Technical Information FOREWORD The Atomic Energy Act directs the Atomic Energy Commission to support and foster research in the field of atomic energy. The Division of Research of the Atomic Energy Commission is responsible for accomplishing this objective in the physical sciences. Research is supported at the AEC National Laboratories, at other Government Laboratories, at universities, at research institutes and foundations and at industrial laboratories. The Chemistry Program is administratively divided into the "on-site" and the "off-site" programs. The "on-site" program is carried out at the SEC Laboratories and other Government-owned facilities. The "off-site" program is carried out elsewhere and consists primarily of research projects performed through contracts with educational institutions. This document summarizes the objectives and current status of the individual research projects supported by the Office of Chemistry Programs of the Division of Research under its "on-site" program. Projects supported at the National Bureau of Standards are also included. It is the purpose of this document to inform the scientific community of the current researches being supported. The summaries have been organized and numbered according to the place where work is carried out. There is also a comprehensive subject index included to permit detailed search for information by subject. Each summary includes the name of the Laboratory at which the work is carried out, the Department or Division, the principal investigator or investigators, and the date on which the summary was received. All of the research presented in this document is unclassified and investigators are encouraged to report their results in the open literature at the earliest opportunity for wide dissemination of the information. The interested reader is referred to Nuclear Science Abstracts or to Chemical Abstracts as sources of information concerning publications resulting from the work summarized in this document. Inquiries or comments concerning the researches described should be directed to: Dr. A. R. Van Dyken Assistant Director of Research for Chemistry Programs Division of Research, USAEC Washington, D. C. 20545 TABLE OF CONTENTS Section Ames Laboratory - Chemistry Division 1A Ames Laboratory - Chemical Engineering Division 1B Argonne National Laboratory - Chemistry Division 2A Argonne National Laboratory - Chemical Engi- 2B neering Division Brookhaven National Laboratory - Chemistry 3A Department Brookhaven National Laboratory - Nuclear 3B Engineering Department Hanford Atomic Products Operation - Hanford 4 Laboratories Lawrence Radiation Laboratory - Berkeley - 5A Chemistry Division Lawrence Radiation Laboratory - Berkeley - 5B Inorganic Materials Research Division National Bureau of Standards 6 University of Notre Dame - Radiation Laboratory 7 North American Aviation - Atomics International 7X Oak Ridge National Laboratory - Chemistry 8A Division Oak Ridge National Laboratory - Analytical 8B Chemistry Division Oak Ridge National Laboratory - Reactor 8C Chemistry Division Oak Ridge National Laboratory - Chemical 8D Technology Division SECTION 1A AMES LABORATORY - CHEMISTRY DIVISION 1Al Electrometric Methods of Analysis 1A2 Investigation of Bifunctional Organophosphorous Com- pounds as Solvent Extractants 1A3 Chemistry of vic dioximes 1A4 Analytical Separations by Reversed-Phase Chromatography 1A5 Analytical Ion-Exchange Separations 1A6 Quantitative Determination of Interstitial Oxygen and Nitrogen Impurities in Metals 1A7 Analytical Emission Spectroscopy 1A8 Atomic and Molecular Absorption Spectra 1A9 Experimental Molecular Structure 1A10 Diffraction Techniques 1All Structural Chemistry 1A12 Interactions of Magnetic Species in Solids 1A13 Thermodynamic Properties and Related Properties of Aqueous Rare-Earth Chloride Solutions 1A14 Studies of Free Radical Reactions and Properties in Solution 1A15 Kinetics and Mechanisms of Inorganic Reactions 1A16 Surface Chemistry 1A17 Physico-Chemical Characterization of Inorganic Com- pounds by Mass Spectrometry 1A18 Instrumentation (Mass Spectrometry) 1A19 Physical and Chemical Properties of Reduced Metal Halides 1A20 Reaction of Metals with Their Molten Halides SECTION 1A Continued 1A21 Phase Relation and Vaporization Reactions at High Temperatures 1A22 Chemical Effects in Nuclear Reactions 1A23 Physical Properties of Silver Halides 1A24 Chemistry of the Platinum Elements 1A25 Separation of Rare Earths by Ion Exchange 1A26 Separation of Light Isotopes 1A27 Determination of Stability Constants of Rare Earth Complex Species 1A28 High Purity Materials Studies Using Activation Analysis for Impurity Determination 1A29 Recoil Chemistry of Carbon-ll For further information on completed work, the reader is referred to the open scientific literature and to the Ames Laboratory Annual Summary Report for July 1962 through June 1963, IS-700, September 1963. 1Al AMES LABORATORY Chemistry Division Charles V. Banks/Motomu Kasagi 1/10/64 George J. Kamin/Michael J. Fahsel ELECTROMETRIC METHODS OF ANALYSIS The sine-wave (A.C.) polarographic method has been found to give quite good results for the determination of small amounts of indium in the presence of large amounts of cadmium, lead, or tin. Niobium and zirconium can be determined in citric acid media with greater sensitivity than is obtainable with D.C. po- larography. It is planned to apply the technique of sine-wave (A.C.) polarography to other cases where D.C. polarography is not suitable. The greater sensitivity of the A.C. method and the fact that much larger ratios of reducible species can be tolerated by the A.C. method than by the D.C. method makes the A.C. polarographic method a powerful analytical technique for the determination of trace impurities in "pure" metals. The interaction of hydrogen ions with 1, 10-phenanthroline is not well understood. Experimental data on this system seem to suggest that poly-1, 10-phenanthroline-hydrogen ion species may exist in solution. It is planned to study this system in some detail to establish more clearly the species that are present in aqueous acid solution, and, if possible, measure the stability constants of these species. A method for the coulometric titration of the alkaline earth ca- tions following the separation of these ions by a reversed-phase chromatographic method was developed. The zones containing the individual cations were cut out and the cation eluted from the paper and titrated coulometrically with electrically generated EDTA. The EDTA was formed by the reduction of the EDTA-Hg complex at a mercury electrode. This technique is being extended to many other cations. Publication 1. Dale and Banks, "Study of Metal-l, 10-Phenanthroline Complex Equilibria by Potentiometric Measurement," Inorg. Chem., 2, 591 (1963). 1A2 AMES LABORATORY Chemistry Division C. V. Banks/J. W. O'Laughlin 1/10/64 J. W. Ferguson/J. E. Mrochek/R. Parker INVESTIGATION OF BIFUNCTIONAL ORGANOPHOSPHORUS COMPOUNDS AS SOLVENT EXTRACTANTS The separation of complex mixtures of elements is often neces- sary before the quantitative analysis of the individual components of the mixture can be made. The solvent extraction technique is one of the most powerful tools available to the analytical chemist for effecting such a preliminary separation. This research in- volves the synthesis and study of a new class of solvent extractants, bifunctional organophosphorus compounds and particularly bis(dialkyl- phosphinyl)alkanes. Information on the nature of the adducts which these compounds form with various cations has been obtained by means of visible and infrared spectroscopic, conductometric, cryoscopic, liquid- liquid partition, and nuclear